New anthraquinone  dyestuffs contain-



United States Patent NEW ANTI-IRAQUINONE DYESTUFFS CONTAIN- ING DIAMINO-TRIAZINYLAMLNO RADICALS Max Staeuble and Kurt Weber, Basel, Switzerland, assignors to Ciba Limited, Basel, Switzerland No Drawing. Filed May 2, 1960, Ser. No. 25,884 Claims priority, application Switzerland May 6, 1959 8 Claims. (Cl. 260-249) This invention provides valuable anthraquinone vat dyestufis which are free from salt-forming groups that impart solubility in water and which correspond to the general Formula 1 in which A represents a vattable radical, m is a whole.

number not greater than 4, n is a whole number not greater than 5, at least three of the radicals R R R and R represents hydrogen atoms or alkyl or cycloalkyl radicals which may be substituted and one of the said radicals represents a hydrogen atom or an alkyl or cycloalkyl radical which may be substituted or a benzene radical, or the radicals R and R or R and R together with the nitrogen atom represent the radical of a heterocyclic ring system, for example, a piperidine or morpholine ring.

As alkyl or cycloalkyl radicals there may be mentioned more especially those containing not more than 6 carbon atoms. The alkyl radicals may be substituted, for example, by halogen atoms or hydroxyl, alkoxy or cyano groups, and are advantageously free fromjamino groups. As examples of suitable alkyl radicals there may be mentioned the methyl, ethyl, propyl, isopropyl, butyl, B-hydroxyethyl, 'y-hydroxypropyl, p-chlonethyl, cyanethyl and ,B-methoxy ethyl groups. A's an'example of a cycloalkyl radical there may be mentioned the cyclohexyl group. The dyestufis must be free ifrom saltforming groups that impart solubility in water, that is to say, sulfonic acid or carboxylic acid groups, or aliphatic amino groups.

This invention also provides a process for the manufac-- ture of the dyestulfs of the above Formula 1 wherein a vattable amine of the Formula 2 in which A and n have the meanings given above, is

condensed with one molecular proportion of a compound of the Formula 3 Ol-C C-X .1 l.

group or an alkylamino, cycloalkylamino, phenylamino or dialkylamino group which may be substituted,- and 3,074,945. Patented Jan. 22, 1963 Y represents a chlorine atom or an amino group or an when the condensation product so obtained contains 1 or 2 chlorine atoms, the chlorine atom or atoms is or are exchanged for an amino, alkylamino, dialkylamino, hy-

droxyalkylamino or phenylamino group or groups, and

wherein the starting materials are so chosen that the final dyestufl contains not more than one phenylamino group.

As vattable amines there may be used monoamine or diamines, for example, l-aminoanthraquinone or a simple substitution product thereof, for example, l-amino- 4-methoxy-anthraquinone or a l-amino-4- or -5- or -8- acylamino-, especially -benzoylamino-, anthraquinone. In the case of a benzoylamino-compound the benzoyl radical may be substituted, for example, by a halogen atomor a methoxy, alkyl, trifiuoro methyl, sulfonamido or sulfone group. Furthermore there may be mentioned 1:4-diamino anthraquinone and 2-substitution products thereof, 1:5- or 1:8-diaminoanthraquinone or 1:5-diamino-4:S-dihydroxyanthraquinone. The radical A in the above Formula 1 includes anthraquinone radicals which contain fused carbocyclic or heterocyclic rings for example, 4-aminoanthraquinone 2:1(N) acridone, 5- amino 1:9 isothiazole anthraquinone, 4- or 5- amino-anthrapyrimidine, amino-acedianthrones, 4- or 5- amino-l':l-dianthrimidecarbazole, 4- or 5-arnino-5-benzoylamino, dianthrimidcarbazole, 4-amino-4 -benzoylamino-dianthrimidcarbazole, 4 amino anthrapyridone,. amino-dibenzanthrone, aminoisodibenzanthrone, aminoanthanthrone, aminobenzanthrone, aminofiavanthrone, aminopyranthrone, and also compounds of the formulae These compounds are condensed with a compound of the Formula 3 for example, with cyanuric chloride. In this case there is obtained a condensation product that contains 2 chlorine atoms in the triazine radical. These chlorine atoms are exchanged for amino groups by re-- action with ammonia or aliphatic amines.

The aminoanthraquinones may also be condensed with dichlorotriazines of the Formula 4- in which R; and R each represent a hydrogen atom or an alkyl group which may be substituted, or not more than one of the radicals R and R represents a benzene radical. The condensation product so obtained, which contains one chlorine atom bound'to the triazine radical, is reacted with ammonia or an aliphatic amine. When R and R both represent an alkyl radical, the condensation product may be reacted with an aminobenzene.

Finally, the aminoanthraquinones may be reacted with monochlorotriazines of the Formula in which R R R and R have the meanings given in connection with Formula 1.

The reaction of the aminoanthraquinone with the triazine of the Formula '3 is advantageously carried out in an inert organic solvent, for example, nitrobenzole, chlorobenzole, or ortho-dichlorobenzole at a raised temperature.

In general it is not necessary to isolate the chlorinecontaining primary condensation products, so that the two reactions may be carried out in the same vessel.

The dyestuffs so obtained are useful for a very wide variety of purposes, especially as vat dyestuifs, pigments or as dispersion dyestuffs for dyeing synthetic fibers. Depending on the size of the anthraquinone radical or the nature of the substituents in the triazine radical, they are better suited for one purpose than another.

Dyestutfs which contain the radical of the formula owing to their good fastness to light and migration, are very suitable as pigments. Dyestuffs which contain as the anthraquinone radical one which consists of not more than three benzene nuclei and, as substituents at the amino groups of the triazine radical, alkyl or hydroxyalkyl groups, are useful as dispersion dyestuffs for synthetic fibers, especially fibers of cellulose ester, polyamides, polyacrylonitrile or polyethylene terephthalate.

Of special interest as vat dyestuffs are those anthraquinones of the Formula 1 in which A represents a higher condensed anthraquinone radical, for example, a pyranthrone, acedianthrone, dibenzpyrenquinone, and especially a dibenzanthrone or isodibenzanthrone radical. Dyestufis which contain the dibenzanthrone radical are vat dyestuffs which dye cellulose fibers valuable deep black tints. Of special interest are dyestufls of the clibenzanthrone series which contain at least one hydroxyalkylamino group in the triazine radical.

The following examples illustrate the invention, the parts and percentages being by weight:

Example 1 chloride in 40 parts of nitrobenzene and thereupon 0.5 part of pyridine are added and the whole is stirred for 12 hours at 170 C., then cooled to room temperature and the cyanuration product of the formula is filtered off and washed with nitrobenzene. The filter cake is added in small portions at to C. to 100 parts of monoethanolamine and the mixture is stirred for another 2 hours at 150 C., then allowed to cool, poured into water, and the dyestulf of the formula erment-on is filtered oif, thoroughly washed with water and then;

with acetone and dried under reduced pressure at 60 When dry, the new dyestufi is a black powder whichv dyes cotton and regenerated cellulose from an alkaline hydrosulfite vat valuable black tints having excellent. properties of fa'stness. v v i The identical dyestuff is obtained when a suspension, heated at C., of the primary cyanuration product in nitrobenzene is treated dropwise Within one hour with 20 parts of monoethanolamine in 20 parts of chloroform and the reaction mixture is stirred on for several hours at 170-180" C.

When the process described in the first paragraph is carried out with N-methyl-aminodibenzanthrone instead of with aminodibenzanthrone, proceeding otherwise in identical manner, a vat dyestufi" is obtained which dyes. cotton brownishblack tints of excellent properties of fastness. i

Example 2 The cyanuration product described in the first paragraph of Example 1, in the form of the suction filter cake, is added in small portions to 100 parts of diethanolamine at 150160 C. with vigorous stirring and the whole is stirred for a further hour. The dyestuff of the formula is isolated as described in Example 1; it'dyes cotton and regenerated cellulose from a reddish blue hydrosulfite vat full black tints of outstanding properties of fastness.

Example 3 6.2 parts of the dichloro-triazine product of aminodibenzanthrone described in Example 1 are suspended in 200 parts of nitrobenzene and the suspension is heated to 160 C. In the course of 2-3 hours 12 parts of cyclohexylamine are then added dropwise and the mixture is stirred for 6 hours at ISO-160 C., allowed to cool, and the dyestuff of the formula is filtered off, washed with nitrobenzene, then with methanol and finally with water, and dried under reduced pressure at 70-80 C.

' The new dyestulf dyes cotton and regenerated cellulose from a reddish blue hydrosulfite vat very fast bluish grey tints.

When in this example, instead of cyclohexylamine, a solution of 5.5 parts of hydroxylamine hydrochloride in 30 parts of pyridine, or 8 parts of hydrazine hydrate in 30 parts of pyridine, is added dropwise, dyestufis are obtained which have similarly good properties.

properties.

6 Example 4 The dichlorotriazine product of aminodibenzanthrone described in the first paragraph of Example 1, in the form of the filter cake still moist with nitrobenzene, is added in small portions to parts of N-methylethanolamine with vigorous stirring at -150 C. and the mixture is stirred for 2 hours at the same temperature. The dyestufl of the formula is isolated as described in Example 1; it dyes cotton and regenerated cellulose from a hydrosulfite vat greenish black tints having very good properties of fastness.

Example 5 The dichloro-triazine product of aminodibenzanthrone described in the first paragraph of Example 1, in the form of the filter cake, is suspended in an autoclave in 200 parts of nitrobenzene and 20 parts of diethylamine and the whole is heated for 12 hours at 100-110 C. The dyestufi of the formula is filtered off, washed with nitrobenzene, then with methanol and finally with water, and driedunder reduced pressure.

The new dyestuff dyes cotton and regenerated cellulose from an alkaline hydrosulfite vat very fast bluish gey to bluish black tints.

When in the above example instead of diethylamine, ammonia is injected in the autoclave up to a pressure of 6-8 atmospheres gauge, the resulting dyestufi has similar 3 Example 6' NH-CHPCHl-Ol Example 7 A suspension of 9.4 parts of aminodibenzanthrone in 200 parts of anhydrous nitrobenzene is heated to 160- 170 C. A warm solution of 7.6 parts of Z-N-methylanilino-4z6-dichloro-1:3:5-triazine in 50 parts of nitrobenzene is added, and in the course of one hour 2.24 parts of N-dimethylaniline are slowly and vigorously stirred in dropwise. The mixture is stirred on for 7 hours at l90200 C., cooled to room temperature, filtered, and the filter residue is washed with nitrobenzene on the filter. The filter cake is then added in small portions to 100 parts of boiling monoethanolamine and stirred on for 2 hours, the whole is poured into water, and the dyestufi of the formula is filtered oil, washed until neutral and dried under reduced pressure at 70-80 C.

The new dyestuft dyes cotton and regenerated cellulose 8 from a hydrosulfite vat black tints having excellent properties of fastness.

When in this example instead of 7.6 parts of Z-N- methylanilino-4 6-dichloro-1 :3 :S-triazine an equimolecular amount of 2-cyclohexylamino-4:6-dichloro-113:5-triazine is used, the resulting dyestuff has similarly good properties. 7

Example 8 9.4 parts of aminodibenzanthrone are reacted with 5.8 parts of 2-dimethylarnino-4:6-dichloro-l23:5-triazine in nitrobenzene as described in Example 7, treated with monoetha'nolamine, and the reaction product is isolated.

The dyestuif of the formula l OH.

NH-CHPCHPOH 50.4 parts of S-amino-l :9-isothiazole-anthrone are condensed in 500 parts of nitrobenzene with 74 parts of cyanuric chloride as described in Example 13 and the resulting product is reacted with ammonia in 1200 parts of nitrobenzene as described in the second paragraph of Example 12 to yield a dyestufi of the formula which produces in plasticized polyvinyl chloride orange dyeings of excellent fastness properties.

Example 10 A mixture of 23 parts of 5:5'-diamino-l:1'-dianthrimide carbazole, 600 parts of nitrobenzene and 37 parts of cyanuric chloride is heated for 20 hours at 160 C. After 4 hours the reaction mixture is treated with 1 part of pyridine, allowed to cool and the reaction product is filtered off, Washed with nitrobenzene and chloroform, and dried under reduced pressure at C.

70 parts of the resulting condensation product in 1200 9 120 parts of nitrobenzene are condensed with ammonia as parts of nitrobenzene with 13 parts of cyanuric chloride described in the second paragraph of Example 12, to yield as described in Example 13 and the resulting product is a dyestuff of the probable formula reacted with ammonia in 500 parts of nitrobenzene as de- NH O scribed in the second paragraph of Example 12, to yield I ll a dyestufi of the formula NH: o I H N l r NH iJ o-Nn, HzN 0 0 NH-d G-NH: /1 i N (IJ which produces on cotton and regenerated cellulose from NH: an alkaline hydrosulfite vat fast rust-brown dyeings. Example 11 15 A mixture of 28.5 parts of bis-para-aminophenylimide i i of perylene-tetracarboxylic acid, 1000 parts of nitrobenzene, 38 parts of cyanuric chloride and 1 part of dimethyl formamide is heated for 17 hours at 190-195 C. and then for 4 hours at ZOO-205 C., allowed to cool to 50 C. and filtered. The filter residue is washed with nitroben- A zene and acetone and dried under reduced pressure at 60-70 C.

16 parts of the resulting condensation product are which produces on cotton and regenerated cellulose from acted with ammonia in 1000 parts of nitrobenzene as dean alkaline hydrosulfite vat fast brown tints. scribed in the second paragraph of Example 12, to yield What is claimed is: a dyestufi of the formula 1. An anthraquinone vat dyestuif which is free from N N 00 00 HiNC ONH NC NHO C-NHs 1K l \00 oo LK 3 l NH! 1115::

which dyes cotton and regenerated cellulose from analkasalt-forming groups imparting solubility in water and line hydrosulfite vat fast red tints. In plasticized polyhi h h h f l vinyl chloride the dyestulf produces red dyeings having good fastness properties. CHEM Example 12 I N R1 22.9 parts of bis-meta-aminophenylimide of perylenetetracarboxylic acid in 1000 parts of nitrobenzene are con- 45 I N densed with 22 parts of cyanuric chloride as described in N the first paragraph of Example 18. 5 parts of the result- 0 Rs ing condensation product in 200 parts of nitrobenzene are 1 stirred with 4.2 parts of N-methylethanolamine for 7 hours at ISO-160 C., allowed to cool and suction-filtered. m The filter residue is washed with nitrobenzene, alcohol and water, and dried under reduced pressure at 100 C., in which A represents a member selected from the group to yield a dyestufi of the formula consisting of pyranthronyl, acedianthrone, dibenzpyren- (3H3 CH; III-CHx-CHzOH HO-CHa-CHa-N t f HOCHz-CHg-N J /tl;IH Nl1-O d-lg-om-omon oo --oo H N N H co -o 0 which produces on cotton and regenerated cellulose from quinone, dibenzanthronyl and isodibenzanthronyl, m is an alkaline hydrosulfite vat strong red dyeings having a whole number of at most 2, n a whole number of at most good fastness properties. v 5, at least 3 of the radicals R R R and R represent When the condensation is performed with monoethamembers selected from the group consisting of hydrogen, nolamine or diethanolamine instead of with N-methyllower alkyl, lower hydroxyalkyl, lower chloroalkyl and ethanolamine dyestufis are obtained having similar propcyclohexyl and one of the said substituents represents a erties. member selected from the group consisting of hydrogen,

Example 13 lower alkyl, lower hydroxyalkyl, lower'chloroalkyl, cyclohexyl and phenyl.v v, v I. 15 parts of aminoacedianthrone are condensed in 250 2. An anthraquinone vat dyestuff which is free from salt-forming groups imparting solubility in water and 4. The dyestuff of the formula which is of the formula NH: N H2 N N/ N a u 1 n NHz- C-NH O NH- C-NH:

in which p is a whole number from 1 to 2. H l

3. The dye'stufi of the formula mN-o CHN g 0 NIH-OHz-CHzOE g 2 NH-JJ o-Nu-om-cmon I 6. The dyestufl of the formula o NH 0 EH9 i5 o Q N N V HzN (I) g -NH:

7. The dyestuft' of the formula N N H1No CNHC N N NH-,-C,% \CNH2 I' ll 7 \QO 11; 4 0 0 TH: I IH;

' 8. The dyestufi of the formula CH3 CH3 Ii-CH OH=OH HO-CHz-QH -Ih' HOOHz-OH2NJJ (J-NH NH-(E -N-OHz-CHzOH 511: N I 6 N 11 5 N N References Cited in the file of this patent 2,742,466 Randall et a1. Apr. 17, 1956 1 2,914,531 Staeuble et a1 .Nov. 24, 1959';

UNITED STATES PATENTS OTHER REFERENCES 1,437,783 Steinbuch a1 5, 1922 Thurston et al.: Journ. of the Am. Chem. Soc., vol. 73, 1,523,308 Steinb uch et al Jan. 13, 1925 '75 v page 2993 (middle of col. 1, cpd. v11 1951 UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,074,945 January 22, 1963 Max Staeuble et a1.

It is hereby certified that error appears in the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Column 7, Example 7, the right-hand side of the formula should appear as shown below instead of as in the patent:

-CI-l Signed and sealed this 29th day of October 1963.

(SEAL) Attest:

- EDWIN L. REYNOLDS ERNEST W. SWIDER Attesting Officer A ti Commissioner of Patents 

1. AN ANTHRAQUINONE VAT DYESTUFF WHICH IS FREE FROM SALT-FORMING GROUPS IMPARTING SOLUBILITY IN WATER AND WHICH HAS THE FORMULA 